A5024492567- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Fullerene Chemistry and Applications
- Advanced Chemical Physics Studies
- Carbon Nanotubes in Composites
- Graphene research and applications
- Synthesis and Properties of Aromatic Compounds
- Boron and Carbon Nanomaterials Research
- Photochemistry and Electron Transfer Studies
- Molecular Junctions and Nanostructures
- Synthesis and Reactivity of Heterocycles
- Electrocatalysts for Energy Conversion
- Crystallography and molecular interactions
- Luminescence and Fluorescent Materials
- Synthesis and Characterization of Pyrroles
- Laser-Ablation Synthesis of Nanoparticles
- Oxidative Organic Chemistry Reactions
- Mass Spectrometry Techniques and Applications
- Organic Electronics and Photovoltaics
- Synthesis and Catalytic Reactions
- Anesthesia and Neurotoxicity Research
- Fuel Cells and Related Materials
- Molecular Sensors and Ion Detection
- Catalytic C–H Functionalization Methods
- Spectroscopy and Quantum Chemical Studies
Lomonosov Moscow State University
2015-2024
Moscow State University
2023
A new umpolung approach to the C3–H functionalization of indoles with diverse nucleophiles based on intermediate formation I(III) reagents is described. The 3,5-dimethylisoxazol-4-yl auxiliary allows for selective indole transfer under catalyst-free conditions, which was impossible using previously reported reagents. Combining mildness transition-metal-free conditions and high reactivity hypervalent iodine reagents, this protocol tolerates various functional groups provides access that are...
A green, scalable, and sustainable approach to prepare aqueous fullerene dispersions (AFD) C60, C70, endohedral metallofullerene [email protected]82, their derivatives C60Cl6, C70Cl10, supramolecular ester-like derivatives, 10 species total, is proposed. For the first time, an immersed ultrasonic probe was used preparing for pristine fullerenes without addends. Both ultrasound-assisted solvent-exchange direct sonication techniques AFD preparation using were tested. The average time decreases...
We report three new isomers of C70(CF3)8, structurally related to p(7)mp-C70(CF3)10, that are inaccessible by direct trifluoromethylation, but can be easily identified among the products transalkylation higher trifluoromethylfullerenes with C70. The reported compounds characterized UV/Vis, 1 D and 2 COSY (19)F NMR spectroscopy, DFT calculations. A rather unusual addition pattern is observed in p(6),i-C70(CF3)8 which one addend attached remotely from others; polarization adjacent unsaturated...
Abstract Novel difluoromethylenated [70]fullerene derivatives, C 70 (CF 2 ) n ( =1–3), were obtained by the reaction of with sodium difluorochloroacetate. Two major products, isomeric mono‐adducts [6,6]‐open and [6,6]‐closed configurations, isolated their homofullerene methanofullerene structures reliably determined a variety methods that included X‐ray analysis high‐level spectroscopic techniques. The isomer constitutes first example non‐hetero derivative in which functionalisation involves...
CF3 -derivatized fullerenes prove once again to be promising scaffolds for regioselective fullerene functionalization: now with the smallest possible addends-hydrogen atoms. Hydrogenation of Cs -C70 (CF3 )8 and C1 )10 by means reduction Zn/Cu couple in presence water proceeds regioselectively, yielding only one major isomer C70 H2 two , whose addition patterns are combined abundant H4 . The observed selectivity is governed electronic structure trifluoromethylated substrates. Interestingly,...
An interaction of N ‐(cyanomethyl)pyridinium salts with vinamidinium perchlorates or enaminones proceeds as a pseudo‐three component process and results in the formation 3‐ 2‐substituted pyrido[2,3‐ b ]indolizine‐10‐carbonitriles, respectively. Optical properties these compounds have been evaluated, revealing effective green light emission fluorescence quantum yields up to 0.81.
Abstract The first experimental evidence that fullerenes react with alkali‐metal trichloroacetates through a nucleophilic addition‐substitution route, yielding dichloromethylenefullerenes as the final products, is reported. intermediates, C 60 (CCl 3 ) − and 70 anions, have been isolated in their protonated forms ortho ‐C )H, well three one para isomer of )H. structures were unambiguously determined by means 1 H, 13 C, H– HMBC NMR spectroscopy along UV/Vis spectroscopy. observed...
Abstract Thermally‐induced CF 2 addition to C s ‐C 70 (CF 3 ) 8 upon reaction with sodium chlorodifluoroacetate is found proceed via the nucleophilic cyclopropanation pathway, possibly a certain involvement of alternative singlet carbene pathway. Of two major isomers characterized by X‐ray diffraction and spectroscopically, less abundant one has [6,6]‐open structure whereas more product [5,6]‐open isomer highly reactive bridgehead sites. Under ambient conditions, its rapid oxidation...
Abstract We survey the structure and electronic properties of family higher trifluoromethylated C 70 (CF 3 ) n molecules with n= 14, 16, 18, 20. Twenty‐two available compounds, which thirteen are newly obtained characterized, demonstrate broad diversity π‐system topologies, enabled us to study interplay between CF addition pattern properties. UV/Vis spectroscopic cyclic voltammetric studies importance exact rather than plain number addends. Of particular interest is skew pentagonal pyramid...
We report synthesis, isolation, and spectroscopic characterization of the novel [5,6]-open C70(CF2) isomer III along with already known [6,6]-closed [6,6]-open isomers I II. The compounds were obtained in a ratio : II = 4 6 1 by means thermal treatment C70 fullerene sodium chlorodifluoroacetate. This product composition is explained use quantum chemical calculations that identify reaction pathway as two-stage nucleophilic cyclopropanation rather than previously postulated carbene addition....
A series of novel highly soluble double-caged [60]fullerene derivatives were prepared by means lithium-salt-assisted [2+3] cycloaddition. The bispheric molecules feature rigid linking the fullerene spheres through a four-membered cycle and pyrrolizidine bridge with an ester function CO2 R (R=n-decyl, n-octadecyl, benzyl, n-butyl; compounds 1 a-d, respectively), as demonstrated NMR spectroscopy X-ray diffraction. Cyclic voltammetry studies revealed three closely overlapping pairs reversible...
C2 -C70 (CF3 )8 was found to be a very promising substrate in the Bingel and Bingel-Hirsch reactions combining perfect regioselectivity with much higher reactivity compared its analogs. The diethyl malonate yield single isomer of monoadduct C70 [C(CO2 Et)2 ] -symmetrical bisadduct ]2 . variation is particularly interesting that it additionally affords, similar regioselective manner, unexpected alkylated derivatives [CH(CO2 ]H ][CH(CO2 ]H. novel compounds have been isolated structurally...
Here we report a reaction of the fullerene derivatives C60Ar5Cl, which enables substitution Cl with thiophene residues and formation novel family C1-symmetrical C60 six functional addends C60Ar5Th. The discovered provided straightforward approach to synthesis previously inaccessible multifunctional water-soluble derivatives, including compounds antiviral activity against human immunodeficiency influenza viruses.
A cyclopropanated derivative of the trifluoromethylated fullerene C s -C 70 (CF 3 ) 8 demonstrates reversible switching behavior triggered by excited state electron transfer or negative charging.
2,3,6,7,10,11-Hexabromotriphenylene (HBTP) and 2,3,6,7,10-pentabromotriphenylene (PBTP) were investigated by means of dissociative electron attachment spectroscopy (DEAS). The dominant decay channel the transient molecular negative ions consists elimination Br– with resonances in low energy region. Formation long-lived parent anions autodetachment lifetime τa = 310 μs is observed at thermal energies. adiabatic affinities, EAa 1.12 ± 0.1 eV HBTP 1.09 PBTP, evaluated using a simple Arrhenius...
We report a comprehensive study of novel isomer C70(CF3)12, p9mp-C70(CF3)12, whose electrochemical behavior differs from most the other trifluoromethylated fullerenes. The addition pattern p9mp-C70(CF3)12 is established by means 19F–19F COSY NMR spectroscopy and DFT calculations. Like p7mp-C70(CF3)10, new undergoes dimerization to [C70(CF3)12]22– upon single-electron reduction. observations are supported calculations energy temperature dependence CW X-band EPR data. Experimentally determined...
Fullerene derivatives with >CH 2 addends in [6,6]‐open or [5,6]‐closed configuration are uncommon of fullerene derivatives, but they readily accessible via treatment C s ‐C 70 (CF 3 ) 8 diazomethane followed by thermolysis photolysis. Both thermodynamic and kinetic factors favor regioselective addition at the near‐equatorial [5,6]‐double bond to give a thermally labile pyrazoline intermediate. Thermal extrusion N from latter is kinetically controlled process orbital symmetry...